Method of simultaneously permanently dyeing and waving human hair



United States Patent Oifice 3,399,682 METHOD OF SIMULTANEOUSLYPERMANENTLY DYEING AND WAVING HUMAN HAIR Toshio Isaji, Aichi-gun,Aichi-ken, Japan, assignor to Kabushiki Kaisha Hoyu Shokai, Higashi-ku,Nogoyashi, Japan, a joint-stock company of Japan No Drawing. Filed Aug.5, 1963, Ser. No. 300,043 7 Claims. (Cl. 132-7) This invention relatesto a method and a preparation of a safe and harmless substance which canbe classified as a hair dye and permanent waving agent which is capableof permanently dyeing keratin, especially human hair, to any desiredcolor tones, simultaneously enabling one to make a permanent wave bywinding it around a rod.

It is an object of the present invention to provide a method ofattaining such a permanent dyeing of keratin, especially human hair,using non-poisonous coal tar dyes which have not been well utilized forsuch purpose under ordinary conditions, without causing any injury tothe keratin, especially human hair, to be dyed, and obtaining a strongadherence of the dye such as not to be sepa rated easily through rubbingor shampooing.

It is another object of the present invention to provide a methodcapable of dyeing keratin, especially human hair, permanently as well asmaking a permanent wave by winding keratin, especially human hair,around a rod at a proper time.

It is another object of the present invention to provide a preparationfor permanently dyeing keratin, especially human hair, to any desiredcolor tone safely and easily by a simple process without causing anyundesirable consequence derived therefrom.

It is still "another object of the present invention to provide apreparation for dyeing keratin, especially human hair, by winding itaround a rod as well as making a permanent wave at a proper time.

Hereinafter this invention will be explained in detail.

This invention is characterized by a process of making a permanent waveby treating keratin to be dyed with a mild alkaline aqueous solutioncomposed of a small quantity of water soluble mercaptans and dyestuffssuch as certified coloring agents or a group of dyestuff made of a kindof coal tar dyestutf which is certified as nonpoisonous (especially suchmetal containing dyestuffs as Neolan dye or Palatine fast dye) or amixture of these, and winding the said keratin around a rod at a propertime to obtain a permanent wave, thereafter treating the same with anacidic substance so as to strengthen the bond between the dyestuif andkeratin, especially human hair, restoring the keratin, especially humanhair, back to its normal condition i.e., isoelectric point in a pH rangeof -6 and also treating the same with an aqueous solution of an oxidizerto strengthen and fix the permanent wave formed on the keratin,especially human hair.

The dyeing method and its preparation contained in this invention havepartly been publicized by Morgan in U.S.P. No. 2,776,668. The mercaptansas being used in this invention and U.S.P. No. 2,776,668 are consideredto aid the permeation and fixation of the dye into the keratin to becolored by transferring the dye directly into the cell structure of thekeratin to be dyed.

However, it is a well known fact that a group of mercaptans consistingof thioglycolic acid, thiosuccinic acid, thiolactic acid and thiophenol,and their derivatives is capable of reducing cystine linkage to cysteinein keratin, and in reality of weakening keratin.

Such functions of mercaptans are influenced especially by theconcentration of the mercaptan, as well as the alkalinity of thesolution, temperature and treating time; and in cases Where any of suchfactors exceed tolerance limit, the keratin will be weakenedconsiderably, result- Patented Sept. 3, 1968 ing in undesirableswelling, twisting or softening thereof.

Therefore, needless to say, it becomes necessary to maintain thesefactors within as mild a condition as possible and at the same time toprevent such disadvantages as described above from happening through adequate after treatment.

This invention is characterized by the following special features asopposed to the USP. No. 2,776,668 by Morgan.

In accordance with this invention mercaptans having a concentration aslow as possible are to be used, and reducing sulfide, urea or thioureaand proteolytic enzyme are to be added as an assistant into aqueoussolution of alkaline mercaptans for the purpose of attaining theintended purpose at a low alkalinity, low temperature and in a shorttreating time.

Alkaline aqueous solutions of reducing sulfide such as ammonium sulfideand sodium sulfide etc. are capable of softening and swelling keratin.

It is well known that urea and thiourea destroy the hydrogen bond ofkeratin, especially human hair, and it is possible to obtain a strongerpermanent wave by adding urea into ammonia-alkalic solution ofthioglycolic acid when compared with cases where no such urea is addedtherein. These substances can make a permanent wave on keratin,especially human hair, even when used alone, although it may take alonger time and a higher room temperature. Thus, it can be recognizedthat the addition of reducing sulfide and urea or thiourea into aqueoussolutions of alkaline mercaptans aids the transfer of coal tar dyes intokeratin, especially human hair, and furthermore is effective inobtaining a stronger permanent wave.

Although a proteolytic enzyme also has a permanent wave effect onkeratin, especially human hair, such effect is only noticeable after aconsiderably long time.

However, when used together with mercaptans, it can act effectively onkeratin, causing the keratin to swell and soften, at the same timemaking possible the permeation of mercaptans resulting in muchimprovement in permanent wave effect, i.e., by addition of a proteolyticenzyme a decrease in the concentration of mercaptans becomes possible.Proteinase such as pepsin, papain, phytin etc. can be cited as effectiveproteolytic enzymes.

These are suitable for the purpose in consideration of the fact that theenzyme action can be restrained by the use of oxidizer in the aftertreatment.

Through the addition of one or more of reducing sulfides, urea orthiourea and the proteolytic enzymes, it becomes possible to obtain amore reliable hair dyeing effect aswell as permanent wave effect usinglower concentration of mercaptans, lower alkalinity and shorter treatingtime, compared with the cases where mercaptans are used alone, andfurthermore it becomes possible to reduce any damaging effect onkeratin, especially human hair.

Among coal tar dyestuffs, especially those which are represented by:

(CI. 14885) Acid Black 54 (Commercial name: Neolan Gray N)chr0miumcomplex derived from (l-a'mino- 6-nitro-2-naphthol-4 sulfonic -acid-1-naphthol-8-sulfonic acid) (01. 18810) Acid Red 186 (Commercial name:Neolan Pink B)chromium complex derived from (l-amino-2-naphthol-4-sulfonic acid- 3-methyl-l-(m sulfophenyl)-5-pyrazolone)(CI. 15711) Acid Black 52 (Commercial name: Neolan Black WA)-chromiumcomplex derived from l-amino-6-nitro-2-naphthol-4-sulfonic acid2-naphthol) (CI. 14880) Acid Black 158 (Commercial name: Palatine FastBlue GGN)chromium complex derived from (1-amino-2-naphthol-4-sulfonicacid- 1-naphthol- 8-sulfonic acid) 3 (CI. 16260) Acid Violet 56(Commercialname: Palatine Fast Violet RNA)-chrornium complex derivedfrom (5-chloro-6-anisidine G-acid) which, being metal containingdyestuffs, either Neolan dye or Palatine fast dye, having composition aschromium complex salt of O-O-dioxyazo compound generally having one ormore sulfonic acid radicals are different from other common acidicmordant dyes in that chrome is already combined with an individualmolecule of dye as a complex compound, the said chrome being consideredto combine with S of cysteine linkage resulted from the reduction ofcystine linkage. At the same time a complex combination is formedbetween the chrome and the basic radical (amino radical) in the keratin.Furthermore, the sulfonic acid radical combines also with the aminoradical in the keratin, therefore it is considered to form anexceedingly strong combination when compared with the other dyes.

As described above, it is the characteristic feature of the presentinvention to select and use such a metal containing dye of a kind ofNeolan dye or Palatine fast dye which is a chrome complex ofO-O-dioxy-azo compound having one or two sulfonic acid radicals. Throughthe use of such dyestuffs, durability and resistivity against therubbing or shampooing are much improved. Furthermore, when the keratin,especially human hair, is treated, after dyeing, with a diluted aqueoussolution of organic acid substance such as tartaric acid, citric acid oracetic acid, it neutralizes the alkali remaining therein and terminatesthe dyeing action. On the other hand, the dye which has penetrated inand combined with keratin, especially human hair, forms a still strongersalt forming combination through the change of the liquid nature, whichintensifies the resistance thereof still more against the rubbing orshampooing. The isoelectric point of keratin, especially human hair, isin a pH range of 5-6, keratin being said to be the strongest near thisrange and the luster thereof is excellent.

This is accomplished by changing the liquid nature of the keratin, whichhas been previously treated with an alkaline mercaptan solution, by suchacidic treatment to transfer the pH to the acidic side, whereby itrecovers its strength, and injury thereof may be prevented.

Such acid treatment is also to be included in the claims of thisinvention.

Furthermore, when keratin which is dyed with a mild aqueous solution ofan oxidizer such as hydrogen peroxide or potassium bromate etc. andthereafter is wound around a rod is treated, it is effective instrengthening the permanent Waves to restore cysteine to cystine throughoxidation of the keratin which has previously been reduced by mercaptansand is also effective in the forming, stressing and fixing of colors incombination with the above mentioned acid treatment. Such treatment withan oxidizer is also to be included in the characteristic features of thepresent invention.

According to this invention, an aqueous solution of one or moremercaptans selected from a group consisting of thioglycolic acid,thiosuccinic acid, thiolactic acid and their derivatives is used, asthioglycolic acid, the amount of the said mercaptan being equivalent toa concentration of 1-7 weight percent of the solution.

However, for the treatment of keratin, especially human hair, pertainingto this invention, a concentration equivalent to 3-5 weight percent ofthe solution as thioglycolic acid, is most adequate.

This invention uses, as an assistant, one or more substances selectedfrom the group consisting of reducing sulfide and urea or thiourea,having an amount equivalent to a concentration of 1-5 weight percent ofthe solution and an enzyme selected from proteolytic enzyme proteinase,having an amount equivalent to 0.1-1 weight percent of the solution.

This invention is to be applied at normal temperature although the mostadequate range is 2025 C.

.In this invention, the pH of the dyeing solution is adjusted within arange of 8-9.6, but the most adequate range of pH for treating keratin,especially human hair, is 9.0-9.5.

To obtain the above pH value, inorganic alkali and organic alkali may beused, but generally concentrated ammonia water and monoethanolamine areconsidered to be adequate.

The process of this invention takes about -60 minutes, and for keratin,especially human hair, 40-50 minutes will be most appropriate.

Each of the above factors, i.e., the concentration of mercaptans,temperature, pH of the solution, and treating time, must be carefullycontrolled, since excess of one or two of these factors can causeundesirable swelling, twisting or softening to keratin, especially humanhair, and can bring about unrecoverable injury.

In order to prevent injury to the keratin, it is necessary, when evenone of the factors has exceeded the applicable range as describedheretofore, to limit one or two of the other factors at a lower range.

The coal tar dyes to be used in this invention have a concentration of0.5-5 weight percent of the solution.

Acidic aqueous solution to be used in the after treatment is a dilutedaqueous solution of an organic acid such an tartaric acid, citric acidor acetic acid, pH of the said aqueous solution being adjusted within arange of 3-4. Furthermore, as to the aqueous solution of the oxidizer tobe used in the after treatment, 1% hydrogen peroxide solution or 3%aqueous solution of potassium bromate is suitable, each treating timebeing 10-30 minutes.

When a certified coloring agent or a coal tar dyestuff which has beencertified as non-poisonous co-exists with the mercaptans, they changegradually, mercaptans also are decomposed, with the result that itseffective concentration will be reduced. It is desirable, therefore, tokeep the alkaline mercaptan solution and the coal tar dyestuif separateand to mix them together at the time of use.

The coal tar dye can be used in the form of a solution containingsurface active agents such assodium alkylbenzenesulfonate oralkylolamide and polyhydric alcohols like propylene glycol andglycerine, and a solvent such as isopropyl alcohol, said additionalsubstances being used with an object of promoting permeability, leveldyeing, dispersibility, and adhesiveness, or otherwise can be used as acompletely dry powder.

The following are examples of the actual application of this invention.

Example 1 Weight Solution A: percent FD & C Blue No. 1 1 FD & C OrangeNo. 1 0.6 FD & C Red No. 2 0.4 Sodium alkylbenzenesulfonate Alkylolamide10 Oleic acid 10 Propylene glycol 13 Isopropyl alcohol 30 Total 100.0

Solution B:

Thioglycolic acid 3 Monoethanolamine 5.25 Thiourea 5 Papain 0.5 Sodiumcarboxymethylcellulose 0.5 Perfume 1.0 Water 84.75

Total 100.0

The above solutions A and B were mixed in the ratio of 1:2 at the timejust before the use (pH=9.4), and was applied onto colorless hair. Thishair was, after 5 minutes, wound around a rod.

After having been kept in the position for 25 minutes, the hair wasrinsed with water in the state of having been kept still around the rod,then 3% aqueous solution of potassium bromate was applied thereon, andafter minutes the hair was removed from the rod, shampooed and then wasrinsed finally with an aqueous solution of tartaric acid (pH=3.5).

The hair was dyed a brownish color and thus a stronger permanent wavewas obtained.

Example 2 Solution A: Weight percent D & C violet No. 1 2

Castor oil sodium sulfate ester 15 Alkylolamide Isopropylalcohol 15Propylene glycol Oleic acid 18 Total 100.0

Solution B:

Ammonium thioglycolate 5 Ammonia water 1.5 Urea 3 Pepsin 1 Sodiumcarboxymethylcellulose 0.5 Perfume 1 Water 88 Total 100.0

The solutions A and B were mixed in the ratio of 1:2 at the timedirectly before the use (pH=9.2). This mixture was applied onto acolorless human hair.

After 10 minutes, the hair was wound around a rod and 25 minutesthereafter was washed with water, and 1% hydrogen peroxide solution wasapplied thereon. The hair was removed from the rod 20 minutes later,followed by a water washing and after-treatment with aqueous solution ofacetic acid (pH=3.8). Thus, the hair was dyed in light purple colorhaving permanent wave thereon.

What is claimed is:

1. A method for the permanent dyeing and waving of human hair comprisingtreating said hair with an aqueous solution containing about 1-7 percentby weight of a water-soluble mercapto compound selected from the groupconsisting of thioglycolic acid, thiosuccinic acid, thiolactic acid, andthiophenol, and about 0.5 to 5 percent by weight of a chromium complexof a O-O' dioxyazo compound having at least one sulfonic acid radical.wherein said chromium complex is selected from the group consisting of achromium complex derived from (l-amino- 6-nitro-2-naphthol-4-sulfonicacid- 1-naphthol-8-sulfonic acid), the chromium complex derived from(l-amin0-2- naphthol-4-sulfonic acid 3-n1ethyl-2- (m-sulfophenyl) -5-pyrazolone), the chromium complex derived from (1- amino 6nitro-2-naphthol-4-sulfonic acid 2-naphthol), the chromuim complexderived from (l-amino-Z-naphthol-4-sulfonic acid 1-naphthol-8-sulfonicacid), the chromium complex derived from (5-chloro-6-anisidine G-acid).

2. The method of claim 1 wherein said mercapto compound is thiosuccinicacid.

3. The method of claim 1 wherein said solution also contains from 0.1 to1 percent by weight of a proteinase.

4. The method of claim 1 wherein said solution also contains from 1 to5% by weight of an agent selected from the group consisting of ammoniasulfide, sodium sulfide, thiourea and urea.

5. The method of claim 1 wherein said human hair is treated with asolution of oxidizer selected from the group consisting of hydrogenperoxide and potassium bromate subsequent to said treatment with saidaqueous solution.

6. The method of claim 5 wherein said solution of oxidizer also containsan acidic material selected from the group consisting of tartaric acid,citric acid and acetic acid.

7. The method of claim 5 wherein said solution of oxidizer has a pH of 3to 4.

References Cited UNITED STATES PATENTS OTHER REFERENCES Merck Index, 5thEdition, Merck and Co., Rahway, NJ. 1940, pp. 593-596.

ALBERT T. MEYERS, Primary Examiner. V. C. CLARKE, Assistant Examiner.

1. A METHOD FOR THE PERMANENT DYEING AND WAVING OF HUMAN HAIR COMPRISINGTREATING SAID HAIR WITH AN AQUEOUS SOLUTION CONTAINING ABOUT 1-7 PERCENTBY WEIGHT OF A WATER-SOLUBLE MERCAPTO COMPOUND SELECTED FROM THE GROUPCONSISTING OF THIOGLYCOLIC ACID, THIOSUCCINIC ACID, THIOLACTIC ACID, ANDTHIOPHENOL, AND ABOUT 0.5 TO 5 PERCENT BY WEIGHT OF A CHROMIUM COMPLEXOF A O-O'' DIOXYAZO COMPOUND HAVING AT LEAST ONE SULFONIC ACID RADICAL,WHEREIN SAID CHROMIUM COMPLEX IS SELECTED FROM THE GROUP CONSISTING OF ACHROMIUM COMPLEX DERIVED FROM (1-AMINO6-NITRO-2-NAPHTHOL-4-SULFONICACID-->1-NAPTHTHOL-8-SULFONIC ACID), THE CHROMIUM COMPLEX DERIVED FROM(1-AMINO-2NAPHTHOL-4-SULFONICACID-->3-METHYL-2-(M-SULFOPHENYL)-5-PYRAZOLONE), THE CHROMIUM COMPLEXDERIVED FROM (1AMINO-6-NITRO-2-NAPTHTHOL-4-SULFONIC ACID<--2NAPHTHOL),THE CHROMUIM COMPLEX DERIVED FROM (1-AMINO-2-NAPHTHOL-4-SULFONICACID-->1-NAPHTHOL-8-SULFONIC ACID), THE CHROMIUM COMPLEX DERIVED FROM(5-CHLORO-6-ANISDINE--> G-ACID).